CN116829620B - Linear block copolymer tougheners with acrylate functionality - Google Patents

Linear block copolymer tougheners with acrylate functionality Download PDF

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CN116829620B
CN116829620B CN202280007262.3A CN202280007262A CN116829620B CN 116829620 B CN116829620 B CN 116829620B CN 202280007262 A CN202280007262 A CN 202280007262A CN 116829620 B CN116829620 B CN 116829620B
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poly
dimethylsiloxane
ether
polydimethylsiloxane
sequence
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CN116829620A (en
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J·刘
A·帕帕达基斯
M·特拉拉沃罗
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Yile Co
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Yile Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Abstract

Embodiments of the present invention provide an acrylate-functionalized polysiloxane-bisphenol a polyether block copolymer that is useful as a toughening agent for thermosetting resins.

Description

Linear block copolymer tougheners with acrylate functionality
Technical Field
The present invention relates to a novel siloxane-bisphenol block copolymer terminated with acrylate functionality that acts as a toughening agent when used with thermosetting resins.
Background
Thermoset resins include epoxy resins, unsaturated polyesters, vinyl esters, phenolics, polyurethanes, silicones, polyamides, and polyamideimides, and are used in a variety of industries for composites, adhesives, and protective coatings. During curing processes involving the application of heat, pressure, ultraviolet (UV) or Electron Beam (EB), individual resin molecules crosslink to form a three-dimensional network, which exhibits high strength, hardness, chemical resistance and thermal stability. However, some cured resins still exhibit inherent brittleness and are therefore still vulnerable to breakage and impact.
To address the brittleness problem of certain resins, a silicone-based toughening agent may be added to the resin prior to curing. For example, U.S. patent publication No. 20200291188 discloses an epoxy-functional polyorganosiloxane toughening agent that, when combined with an epoxy-based thermosetting resin, renders the cured composite less susceptible to breakage and impact damage. However, these epoxy-functional polyorganosiloxane toughening agents have limited reactivity with non-epoxy-based thermosetting resins (such as vinyl esters, unsaturated polyesters, or acrylate-functional resins).
Thus, there is a need for a toughening agent that can chemically react with non-epoxy based thermosetting resins during the curing stage to form a permanent bond between the toughening agent and the resin matrix.
Disclosure of Invention
Embodiments of the toughening agents of the present invention include polysiloxane-alkyl bisphenol a polyether block copolymers capped with acrylate functionality. Embodiments of the toughening agents of the present invention may be combined with an unsaturated thermosetting resin such that during crosslinking or curing, the toughening agent and the resin chemically react to form a permanent bond between the toughening agent and the resin matrix, imparting higher fracture and impact resistance to the resulting product. In addition, the toughening agents of the present invention exhibit better compatibility with unsaturated thermosetting resins, which provides better storage stability for the composite material prior to curing or crosslinking. In addition, the tougheners of the present invention have lower viscosities than other existing tougheners, which improves their processability for mixing and wetting with pigments, fillers, fibers and substrates. In addition, the toughening agent is combined with thermosetting resin, and is suitable for EB and UV curing. In addition, embodiments of the present invention may also be used as toughening agents for other types of thermosetting resins, including but not limited to saturated epoxy resins.
Without limiting the implementation of the toughening agents of the present invention to any particular mechanism, the toughening agents of the present invention may gradually disappear during curing or crosslinking and form separate microphases throughout the resin, forming chemical linkages between the microphases rich in toughening agent and the resin matrix.
Brief description of the drawings
Fig. 1 shows a general structure of an embodiment of the present invention.
FIG. 2 identifies R in FIG. 1 for three embodiments of the invention 1 、R 2 、R 3 Values of x, y and z.
FIG. 3 shows the composition and performance test results of an embodiment of the present invention when combined with a vinyl ester thermosetting resin.
Fig. 4a-4e show the performance test results of fig. 3 in bar graph format.
Fig. 5 shows the composition and performance test results of an embodiment of the present invention when combined with an epoxy thermosetting resin.
Fig. 6a-6e show the performance test results of fig. 5 in bar graph format.
Detailed description of the preferred embodiments
In the following embodiments of the invention, the polymer segments are expressed in terms of the number of repeating monomer units. These numbers should be interpreted to mean the statistical average number of monomer units per molecule rather than the exact numerical requirements.
Embodiments of the toughening agent 100 of the present invention include a linear block copolymer 110 capped at both ends with an acrylate 120. The linear block copolymer 110 includes repeating units of polydimethylsiloxane 130 and bisphenol a poly (ethylene oxide) dialkyl ether 140. Fig. 1 shows the general structure of a toughening agent 100, wherein:
R 1 is H or CH 3 。
R 2 Is an alkyl group having 2 to 3 carbons.
R 3 Is an alkyl group having 2 to 3 carbons.
x represents the number of repeating dimethylsiloxane units and ranges from 1 to 300.
y represents the number of repeating ethylene oxide units ranging from 1 to 100.
z represents the number of repeating polydimethylsiloxane-bisphenol a poly (ethylene oxide) dialkyl ether units ranging from 1 to 100.
Synthesis of the preferred embodiment
The polydimethylsiloxane and bisphenol a poly (ethylene oxide) bis allyl ether can be synthesized in any manner known to those of ordinary skill in the art. The linear block copolymer may be synthesized, for example, by the following steps: 10 to 30 grams of the hydride terminated polydimethylsiloxane, 70 to 90 grams of bisphenol a poly (ethylene oxide) bis allyl ether, and 0.01 to 0.1 grams of chloroplatinic acid were combined in a reaction vessel, the mixture was purged with N2 gas, and then heated to 120 ℃ for one hour to produce the hydrogenated silicon terminated linear block copolymer. The toughening agent can be synthesized, for example, by the following steps: 60 to 95 grams of the hydrogenated silicon end-capped linear block copolymer, 5 to 40 grams of allyl methacrylate, 0.1 to 1 gram of p-Methoxyphenol (MEHQ) or phenothiazine, and 0.01 to 0.1 gram of chloroplatinic acid were combined, and the mixture was heated to 100 ℃ until all of the hydrogenated silicon functional groups had been converted to acrylate, as determined by monitoring the disappearance of the hydrogenated silicon peaks using fourier transform infrared spectroscopy.
By varying the length of the hydride terminated polydimethylsiloxane and its ratio to bisphenol a poly (ethylene oxide) bis allyl ether during the polymerization step, the inventors identified three preferred embodiments having the structural features shown in fig. 2.
The toughening agent of the present invention is used together with vinyl ester resin
To demonstrate the reinforcing properties associated with the use of the inventive toughening agent with vinyl ester resins, the inventors used the inventive toughening agent shown in FIG. 2 and under the trade name HetronCommercially available common vinyl ester resins were prepared in various proportions to test samples. The inventors added 1.5 g Methyl Ethyl Ketone Peroxide (MEKP) as an initiator, and then cured the compound at room temperature for 24 hours, followed by curing at 100 ℃ for 4 hours. The inventors then conducted a series of industry standard tests to determine various toughness characteristics of the cured compounds, including the following:
critical stress intensity factor (K1 c)
Critical strain energy release rate (G1 c)
Tensile strength of
Elongation percentage
Young's modulus
Visual appearance before curing
Visual appearance after curing
Comparative impact resistance (1=worst, 5=best)
The table of fig. 3 shows the numerical results of ten sample formulations and testing the formulations; fig. 4a-4e show the test results in bar graph form. It can be seen that different formulations of the toughening agents of the present invention result in different effects on various toughness properties, indicating that changing the formulation can result in an overall toughening improvement or an improvement optimized for a particular toughness property.
The toughening agent of the present invention is used together with epoxy resin
In addition to the use of the inventive tougheners with unsaturated thermosetting resins, embodiments of the inventive tougheners have also proven useful in enhancing the toughness performance of epoxy-based resins. To demonstrate this, the inventors prepared ten sample formulations in different proportions using the tougheners of the invention and bisphenol a diglycidyl ether epoxy resin (commonly referred to as DGEBA or BADGE) shown in fig. 2. By way of comparison, the inventors have also prepared two sample formulations, one under the trade name, using commercially available toughening agents1300X 8A commercially available carboxyl-terminated butadiene-acrylonitrile copolymer containing pendant carboxyl functions, the other being under the trade name +.>XT100 commercially available methyl methacrylate-butadiene-styrene. The present inventors added 13 g of triethylenetetramine (TETA) as an initiator, and then cured the compound at room temperature for 24 hours, followed by curing at 100 ℃ for 4 hours. The inventors then conducted the same industry standard tests to determine the various toughness characteristics of the cured compounds. The table of fig. 5 shows twelve sample formulations and the numerical results of testing the formulations; fig. 6a-6e show the test results in bar graph form. It can be seen that different formulations of the toughening agents of the present invention result in different effects on various toughness properties, indicating that changing the formulation can result in an overall toughening improvement or an improvement optimized for a particular toughness property.
Additional embodiments
The toughening agent 100 of the present invention described in the foregoing embodiments of the present invention may be modified and/or extended by one of ordinary skill in the art without departing from the spirit of the present invention, as long as the toughening agent: (a) enhancing one or more toughness properties (e.g., critical stress intensity factor, critical strain energy release rate, tensile strength, elongation, young's modulus, and impact resistance) when combined with a thermosetting resin (b) can be stably stored with the thermosetting resin prior to curing, (c) has a sufficiently low viscosity to maintain processability, and (d) is still suitable for EB and UV curing.
Some preferred embodiments identify specific resins, however, the toughening agents of the present invention may be used with other resins known to those of ordinary skill in the art, including but not limited to vinyl esters, unsaturated polyesters, acrylate functionalized resins, epoxy resins, and polyurethanes.
Certain curing techniques, initiators, and curing agents are identified in some preferred embodiments, however other curing techniques and components known to those of ordinary skill in the art may be used depending on the choice of resin and application.
Some preferred embodiments impose specific limitations on the number of monomer units (i.e., the values of x, y, and z in fig. 1) of the polymeric component, however, other embodiments of the toughening agent 100 of the present invention may use the full disclosed polymerization range, depending on the application and desired toughness properties.
The structure of the tougheners of the present invention, as shown in fig. 1, requires specific terminal functional groups and linear block copolymers, however, other functional groups may be added to the toughener 100 to provide other characteristics or attributes.
The proportions of resin and toughener shown in fig. 3 and 5 are merely exemplary, and one of ordinary skill in the art can create compounds having other proportions within the scope of the present disclosure without undue experimentation. Furthermore, one of ordinary skill in the art may combine additional components with these formulations, including but not limited to additional toughening agents, pigments, fillers, fibers, flame retardants, and defoamers.
The structure of the toughening agent 100 of the present invention, as shown in fig. 1, includes polyethylene oxide ethers, however, other short ether polymers such as polypropylene oxide ethers and polybutylene oxide ethers, or combinations of these ethers, may be used.
In some preferred embodiments, the acrylate functionality is propyl methacrylate, however in other embodiments the acrylate functionality may be another acrylate, including but not limited to ethyl methacrylate, ethyl acrylate, and propyl acrylate.

Claims (24)

1. A toughening agent for a thermosetting resin, comprising:
a linear block copolymer comprising a plurality of poly (ethylene glycol) units (AB) z Alternating units of a-a sequenced polydimethylsiloxane and bisphenol a poly (ethylene oxide) dipropyl ether, wherein a is the polydimethylsiloxane, B is the bisphenol a poly (ethylene oxide) dipropyl ether, and z is a number from 1 to 100; and
two acrylate functional groups, one at one end of the linear block copolymer and the other at the other end of the linear block copolymer.
2. The toughening agent according to claim 1, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x is a number from 1 to 300.
3. The toughening agent according to claim 1, wherein
Each acrylate functional group has the formula CH 2 R 1 COOR 2 -, wherein R is 1 is-H or-CH 3 And R is 2 is-CH 2 CH 2 -or-CH 2 CH 2 CH 2 -。
4. The toughening agent according to claim 1, wherein
The polyethylene oxide ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y is a number from 1 to 100。
5. The toughening agent according to claim 1, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 1;
the polyethylene oxide ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=2; and is also provided with
Each acrylate functional group is propyl methacrylate.
6. The toughening agent according to claim 1, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 2;
the polyethylene oxide ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=4; and is also provided with
Each acrylate functional group is propyl methacrylate.
7. The toughening agent according to claim 1, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 4;
the polyethylene oxide ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=8; and is also provided with
Each acrylate functional group is propyl methacrylate.
8. A toughening agent for a thermosetting resin, comprising:
linearity ofA block copolymer comprising a plurality of monomers- (AB) z Alternating units of a-a sequenced polydimethylsiloxane and bisphenol a poly (ethylene oxide) diethyl ether, wherein a is the polydimethylsiloxane, B is the bisphenol a poly (ethylene oxide) diethyl ether, and z is a number from 1 to 100; and
two acrylate functional groups, one at one end of the linear block copolymer and the other at the other end of the linear block copolymer.
9. The toughening agent according to claim 8, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x is a number from 1 to 300.
10. The toughening agent according to claim 8, wherein
Each acrylate functional group is propyl methacrylate.
11. The toughening agent according to claim 8, wherein
Each acrylate functional group is propyl acrylate.
12. The toughening agent according to claim 8, wherein
The polyethylene oxide ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y is a number from 1 to 100.
13. A resin system comprising:
an unsaturated thermosetting resin;
an initiator; and
a toughening agent comprising:
a linear block copolymer comprising a plurality of poly (ethylene glycol) units (AB) z Alternating units of a-sequenced polydimethylsiloxane and bisphenol a poly (ethylene oxide) dipropyl ether, wherein a isThe polydimethylsiloxane, B is the bisphenol a poly (ethylene oxide) dipropyl ether, z is a number from 1 to 100; and
two acrylate functional groups, one at one end of the linear block copolymer and the other at the other end of the linear block copolymer.
14. The resin system of claim 13, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x is a number from 1 to 300;
each acrylate functional group is a methacrylate;
the ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y is a number from 1 to 100.
15. The resin system of claim 13, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 1;
the ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=2; and is also provided with
Each acrylate functional group is propyl methacrylate.
16. The resin system of claim 13, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 2;
the ether is in the form of (-O-CH) 2 -CH 2 -) y -a sequence arrangement of O-, wherein y = 5;
z=4; and is also provided with
Each acrylate functional group is propyl methacrylate.
17. The resin system of claim 13, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 4;
the ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=8; and is also provided with
Each acrylate functional group is propyl methacrylate.
18. The resin system of claim 13, wherein
The unsaturated thermosetting resin is a vinyl ester thermosetting resin.
19. A resin system comprising:
a thermosetting epoxy resin;
a curing agent; and
a toughening agent comprising:
a linear block copolymer comprising a plurality of poly (ethylene glycol) units (AB) z Alternating units of a-a sequenced polydimethylsiloxane and bisphenol a poly (ethylene oxide) dipropyl ether, wherein a is the polydimethylsiloxane, B is the bisphenol a poly (ethylene oxide) dipropyl ether, and z is a number from 1 to 100; and
two acrylate functional groups, one at one end of the linear block copolymer and the other at the other end of the linear block copolymer.
20. The resin system of claim 19, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -two of the sequence arrangementA methylsiloxane unit, wherein x is a number from 1 to 300;
each acrylate functional group is a methacrylate ester,
the ether is prepared by (OCH) 2 CH 2 ) y A sequence arrangement of O-, wherein y is a number from 1 to 100;
21. the resin system of claim 19, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x is a number from 1 to 300;
each acrylate functional group is an acrylate,
the ether is prepared by (OCH) 2 CH 2 ) y A sequence arrangement of O-, wherein y is a number from 1 to 100;
22. the resin system of claim 19, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 1;
the ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=2; and is also provided with
Each acrylate functional group is propyl methacrylate.
23. The resin system of claim 19, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 2;
the ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=4; and is also provided with
Each acrylate functional group is propyl methacrylate.
24. The resin system of claim 19, wherein
The polydimethylsiloxane includes a plurality of poly (dimethylsiloxane) s 3 ) 2 O)) x Si(CH 3 ) 2 -a sequence of dimethylsiloxane units, wherein x = 4;
the ether is prepared by (OCH) 2 CH 2 ) y O-, wherein y = 5;
z=8; and is also provided with
Each acrylate functional group is propyl methacrylate.
CN202280007262.3A 2022-04-22 2022-04-22 Linear block copolymer tougheners with acrylate functionality Active CN116829620B (en)

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US5691444A (en) * 1995-12-06 1997-11-25 Clemson University Functionalized crystalline polylactones as tougheners for thermosetting resins
CN101056936A (en) * 2004-11-10 2007-10-17 陶氏环球技术公司 Amphiphilic block copolymer-toughened epoxy resins and powder coatings made therefrom
CN103906793A (en) * 2011-08-01 2014-07-02 氰特科技股份有限公司 Thermoset resin compositions with increased toughness
CN106433536A (en) * 2016-09-20 2017-02-22 湖南固特邦土木技术发展有限公司 Dual-curing epoxy resin-vinyl ester resin adhesive used for leaking stoppage and reinforcement of underground engineering fracture
CN109232896A (en) * 2017-07-11 2019-01-18 中国石油化工股份有限公司 A kind of epoxy resin toughener and its preparation method and application
CN111171253A (en) * 2020-03-03 2020-05-19 深圳市勇泰运科技有限公司 Preparation method of toughened epoxy resin and underfill
CN112877016A (en) * 2021-02-03 2021-06-01 辽宁省交通规划设计院有限责任公司 Flexible epoxy resin adhesive and application thereof

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US7767757B2 (en) * 2005-01-20 2010-08-03 Arkema France Thermoset materials with improved impact resistance
US11518854B2 (en) 2019-03-13 2022-12-06 Ele' Corporation Epoxy-functionalized polyorganosiloxane toughener
US20220411561A1 (en) * 2019-07-19 2022-12-29 Arkema France Curable compositions useful for obtaining non-sensitizing cured products

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691444A (en) * 1995-12-06 1997-11-25 Clemson University Functionalized crystalline polylactones as tougheners for thermosetting resins
CN101056936A (en) * 2004-11-10 2007-10-17 陶氏环球技术公司 Amphiphilic block copolymer-toughened epoxy resins and powder coatings made therefrom
CN103906793A (en) * 2011-08-01 2014-07-02 氰特科技股份有限公司 Thermoset resin compositions with increased toughness
CN106433536A (en) * 2016-09-20 2017-02-22 湖南固特邦土木技术发展有限公司 Dual-curing epoxy resin-vinyl ester resin adhesive used for leaking stoppage and reinforcement of underground engineering fracture
CN109232896A (en) * 2017-07-11 2019-01-18 中国石油化工股份有限公司 A kind of epoxy resin toughener and its preparation method and application
CN111171253A (en) * 2020-03-03 2020-05-19 深圳市勇泰运科技有限公司 Preparation method of toughened epoxy resin and underfill
CN112877016A (en) * 2021-02-03 2021-06-01 辽宁省交通规划设计院有限责任公司 Flexible epoxy resin adhesive and application thereof

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CN116829620A (en) 2023-09-29
EP4288482A1 (en) 2023-12-13
US20230340208A1 (en) 2023-10-26
US20240043625A1 (en) 2024-02-08
US11814485B1 (en) 2023-11-14
WO2023204820A1 (en) 2023-10-26

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